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Documente Profesional
Documente Cultură
1957
Recommended Citation
Lane, William James, "Metal-indicator systems in (ethylenedinitrilo) tetraacetic acid titrations " (1957). Retrospective Theses and
Dissertations. 2224.
https://lib.dr.iastate.edu/rtd/2224
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METAL-INDICATOR SYSTEMS IN
(ETHHEHEDINITRILO)TETRAACETIC ACID TITRATIONS
by
Approved:
In Work
d of Major D artm
1 -. _ - _.liege
TABLE OF CONTENTS
Page
INTRODUCTION 1
7-CL-NAPHTHYLAZO)-5-SULF O-8-HYDROXYQUINOLINEj
NAPHTHYL AZOXINE 21
Reagent 21
Titrations of Metals 22
Solutions 23
Titrations
Masking of upany1 ion 27
Related information 27
Spectrophotometries Data and Titrations 29
Equipment 29
Interpretation of spectra 29
Photometric titrations 31
Formation constant 37
Discussion 39
2-(2-HYDR0XÏ-3,6-DISUEP0-1-NAPHTHYLAZ0)-
BENZENEARSONIC ACID; THORIN 1(1
Reagent Ip.
Titration of EDTA with Lanthanum );?
Solution preparation and standardization 1|2
Conditions Ij3
Procedure )|)|
Results %
Interferences 46
Cations Lj£
Anion i|£j
Determination of Metals i]_9
Rare earths I4.9
Other metals 50
Bismuth 51
Cadmium 52
Cobalt 53
Copper 53
Nickel 51).
iii
Summary 99
Suggestions for Further Work 100
BIBLIOGRAPHY 103
ACKNOWLEDGMENTS HI
1
INTRODUCTION
7-(l-NAPHTHYLAZ0)-5-SUIF0-8-HYDR0XYQ.UIN0LINE:
NAPHTHYL AZOXINE
Reagent
SO3K
^_j
\ /y
Titrations of Metals
Solutions
EDTA was prepared by dissolving the proper amount of
disodium or diaramonium salt in water to make a 0.05 M solu
tion. This was standardized by the titration of a standard
zinc solution at pH 10 using Eriochrome Black T indicator.
All metal solutions were made 0.05 M.
Copper, nickel and zinc solutions were prepared by dis
solving weighed amounts of the metals. The copper was
cleaned copper wire. Nickel used was C. P. shot with 0.05%
total listed impurities. Zinc metal was better than 99.9^
pure by spectrographic analysis. An aliquot of this copper
solution was diluted tenfold to serve as the copper blank
solution for some of the titrations.
Cadmium solution was prepared from reagent-grade cadmium
nitrate which was standardized by EDTA titration using a
zinc blank and Eriochrome Black T indicator.
21».
Titrations
The titrations were carried out according to this gen
eral procedure. Aliquots of approximately 0.5 millimoles
were taken for titration with 0.05 M EDTA. The sample was
diluted to 100 ml. Ammonium acetate was used as a buffer
25
for the pH 3*5 region and was added as the solid. From 1
to 2 grams sufficed. The pH was checked with a meter and
adjusted with ammonia or nitric acid. For titrations of
copper at pH It- or of thorium at pH 3.0 to 3*5, sodium
formate or sodium chloroacetate were used respectively.
Masking agents if desired were added. About 10 drops of
0,2% naphthyl azoxine were used. Personal preference and
the color of the solution itself could make a different
amount of indicator desirable. When the copper blank was
required to provide a sharp end-point, 1.00 ml. of 0.005 M
solution was usually added when the titration was about
95/8 completed. Often, the end-point without copper was
noted, then the copper was added and the titration was
carried to the second end-point. The end-point was taken
when the solution had attained the maximum red color. When
the copper blank was included, the maximum, color change was
taken if the blank correction were also determined in this
manner.
The results of the titrations are given in Table 1.
Figures in both columns "No copper added" and "Copper added"
mean that the end-point of the titration was noted, and then
the copper blank was added. The titration was continued
to a second end-point and the value of the copper blank was
subtracted. When end-points were obtained both ways, they
were in good agreement. The blank values for 1.00 ml. of
0.004-9 M copper were well confirmed. The differences
26
Related information
Associates also working with Naphthyl Azoxine indicator
have investigated other interferences and masking agents.
Fritz, Lane and Bystroff (61) found that calcium and
28
Equipment
Absorption spectra were obtained from a Gary Model 12
recording spectrophotometer• Two Cor ex cells of 2.01 cm.
path length were used. Photometric titrations were con
ducted with a Beckman Model DU spectrophotometer. The ti
tration assembly was that built by Klingman, Hooker and
Banks (88). The photometric titration beakers were of
borosilicate glass and had a light path length of about 4
cm.
Interpretation of spectra
The spectra of Naphthyl Azoxine at pH 4-, 6, and 8 are
given in Figure 1. The isobestic point at $12 mp. indicates
that there are two species of the indicator in equilibrium.
Other spectra have shown that the peak of the acid form at
pK 1 and 2 developed prominantly at 54-0 to 550 mp. The
peak of the basic form at 4-80 mp, continued to rise with pH
to pH 11. The molar extinction coefficient for the indicator
at 500 mp, and pH 6 is 13,000.
30
A 04—
600
Photometric titrations
Photometric titrations were undertaken both to use the
technique for dilute titrations and to study the end-point
reaction. To compare photometrically determined end-points
with visual titrations, a number of similar titrations were
made both ways. For both types, the same 5 ml. micro-buret
400 500 600
rr\fJL
Figure 2. Spectra of 10™^ M copper plus Naphthyl Azoxine: curve 1, 1:1; curve 2,
1:2j curve 3, 1:3 mole ratios vs. water and curve 2', 1:2 and curve 3',
1:3 mole ratios vs. 1 equivalent mole blank, 2.01 cm. cells
33
.8-
.5-
.09-
.08-
.07-
.06-
.05
.03-
.02
ML. visually
0.986 0.991 0.989-0.993 0.991-0.999
Average 0.992
Ml. photometrically
44-0 my. 4-52 my, 500 my.
1.000 1.003 0.985
Average 0.996
35
0.900
0700
A
0500-
CUOÛ-
<>-• .Q.—— '—
aoao-
Figure 4.. Photometric titrations of 100 ml. 0.99 x 10"*^ M copper with
1.0 x 10~2 M EDTA
37
at 452 and 440 rap, start their descent at 0,85 ml= , and the
extrapolated end-points are at 1.0 ml. The extrapolations
of the rising portion of the 500 my, curve with the hori
zontal portions intersect at 0.7 and 1.0 ml. The rounded
portions would be due to dissociation of the various com
plexes.
The phototitrations of Figure 5 were mole ratio type
titrations in which 3 x 10 millimoles of Naphthyl Azoxine
were titrated with 5 x 10 ^ M copper solution. The forma
tion of a 1:2 complex would produce a break at 0.3 ml., of
a 1:1 complex at 0.6 ml. The breaks came at 0.20 ml. at
452 my. and at 0.25 ml. and 0.6 ml. at 440 my,, and curvature
started at 0.25 ml. at 500 nqi.
Formation constant
The method of Harvey and Manning (73a) of determining
dissociation constants of complexes from their mole-ratio
plots has been adapted to data from the absorption spectra
of copper-Naphthyl Azoxine complexes. Absorbances were
taken from the maxima of curves 2 and 3' of Figure 2, p. 32.
Absorbance of curve 2 was assumed to be due to the 1:2
complex as dissociated when the reactants were in stoichio
metric proportions. Absorbance of curve 3' was assumed to
be due to the complex when driven toward complete associa
tion by a 50% excess of indicator, but which excess had been
compensated in the blank. Therefore, a, the degree of
1.100-
I.OOO-
Q90C- 440 mu
0700-
0600
0500-
v>
0.400-
oo
0300-
0200-
OIOO
0.000-
0 0.10 0.20 030 040 050 060 0 70 0.80 Q90 1.00 110 130 1.40 |50
ml. Cu*2
Figure 5. Photometric titrations of 100 ml. 3.0 x 10™^ M Naphthyl Azoxine with
4.9 x 10*"^ M copper
39
Kf = (2.2)
f i|xx c k-aro
Discussion
reactions are
KCUY
K (2.5)
KCU(M)
2-(2-HYDROXY-].6-DISULF O-1-NAPHTHYLAZ0)-
BENZENEARSONIC ACID; THORIN
Reagent
H<tS/
Conditions
Although the pink complex exists from pH 3 to pH 6.5
where lanthanum hydroxide precipitates, the optimum range was
found to be pH 5«5 to 6.5* A sharper end-point in fairly
clean solutions occurred at pH 6 but higher amounts of di
verse ions or the addition of organic solvents required lower
pH 5.0 to 5*5 for best color transitions.
Sodium bicarbonate was superior to sodium or ammonium
acetate as a buffer and pH adjusting reagent. It has been
found generally that carboxylic acids tend to interfere with
metal indicator reactions. Possibly an amine buffer might
be superior to bicarbonate.
No change in the end-point transition was noted when
0.25 to 0.50 millimoles of EDTA was diluted to 25, 50, or
100 ml. for titration.
Use of 50fo non-aqueous solvent had no effect other than
requiring the lower apparent pH 5 for the optimum color change.
144
Procedure
This general procedure for the titration was followed.
The desired amount of EDTA was added to water or to the
solution of the cation to be determined and diluted to 50-
100 ml. solution. Two drops of 0«5% Thorin solution were
added. With stirring, about 95% of the amount of lanthanum
required was added. The solution was adjusted to pH 6.5 to
7.0 with sodium bicarbonate. The titration was resumed and
the equivalence point was taken at the first permanent
change from yellow to amber or pinkish orange. Over titra
tion was indicated if enough lanthanum-Thorin complex formed
to make a pink or red solution.
Results
The EDTA solution was freshly standardized against zinc
to be 0.05082 M and lanthanum solution was 0.04143 M by
weight of the oxide dissolved. Aliquots of eight ml. each
of EDTA were titrated with the lanthanum as the pH was varied
(Table 4)* In addition, with reagents diluted to 0.01 M, a
titration calculated to require 9.92 ml. took 9.92 and 9.91
ml.
The diverse-ion effect rendered the end-point less
sharp at concentrations greater than 0.25 M in NH^NO^. The
results of these titrations are also included in Table 4.
45
Interferences
Cations Most cations interfere with the titration.
This was determined by titrating a solution of 1|,00 ml.
EDTA and five drops of 0.1 M solution of each cation added.
The theoretical end-point was 4.91 ml. A titration of
about lj..3 ml, would indicate approximately stoichiometric
interference, The effects of cations are listed in Table
5.
Thus lithium, silver, barium, magnesium and strontium
do not interfere, and calcium causes a slightly low titra
tion. Calcium, of the alkaline earths, seems to be on the
border-line of interference. These titrations were done
at pE 6.0, a lower pH might eliminate the interference of
calcium since interference probably occurs by the forming
a complex with the EDTA. The mole ratio of added cation to
EDTA was 1:8.
Anion In contrast to the many cation interferences,
only a few anions interfere in the titration of EDTA with
lanthanum. Anion interference was checked in a manner simi
lar to that for cations - a 2.00 ml. aliquot of EDTA con
taining 5 drops of 0.1 M anion solution was titrated with
lanthanum. Only citrate, oxalate, and phosphate interfered
with this titration. Results are included in Table 6. A
supplementary test of several anions was conducted by adding
10 drops of the anion to a lanthanum solution, then adding
a measured excess of EDTA and titrating the excess with
47
WV
Fe•3 4.28 ^
Zn+2 4.33
Hf0+2 4.36
Zr0+2 4.75
Hg+2 4.35
aSalts
added mostly as perchlorates, some as chlorides
or nitrates, except as noted.
48
Cyanide o.£o
Sulfate 0.48
Tartrate 0.49 (poor end point)
Fluoride 0.82
Succinate O.48
Determination of Metals
Bare earths
Only the lower rare earths form pink complexes with
Thorin, but back titration of the excess EDTA with lanthanum
has been successfully applied to the determination of other
rare earths. Although it is not a necessity, the formation
constant of 1anthanum-BDTA being the lowest of all the rare
earths makes the reaction more direct.
Rare earth solutions were prepared as standard from
column-purified oxides at least 99.9% pure by spectrographs
analysis. The oxides were ignited to constant weight to
eliminate carbonate as well as water before being dissolved
in perchloric acid. Solutions were prepared of lanthanum,
5o
Other metals
The lanthanum titration of an excess EDTA was success
fully applied to the determination of bismuth, cadmium,
cobalt, copper, nickel, lead, thorium, and zinc. Titrations
could not be obtained for chromic, gallic, ferric, manganous,
mercuric or stannic ions. Aliquots of standardized solutions
5x
+3 +3
MY™~^+Y~^+Ind~%—». Mïm"i{-+LaY"1+Ind*;S—•»• MYm~^+LaY~1+LaInd3"n
(yellow) (yellow) (red)
(3.1)
llj, with the results and are described below. A first set
of ten titrations resulted in the result of 113.2 t 0.2 mg.
thorium found when 112.5 mg. were taken. The difference of
0.6% was unsatisfactory but the precision of only 0.2 mg.
or 0.2% was acceptable. The error cannot be readily ex
plained since the thorium was standardized with excellent
precision, by EDTA titration using the Alizarin Red S pro
cedure of Fritz and Ford (60). Therefore, these two re
agents should be correct relative to one another at least.
Deviation of the lanthanum reagent should not be significant
since in this type of back titration, a 1% error in the con
centration of the titrant would cause only about 0.1% in the
final results if the back titration was less than 1 ml. when
the total EDTA was ten ml. of a similar concentration.
However, these titrations demonstrated that pH 4*5 to
5.0 provided a better color transition than at higher pH's.
In addition several attempts to titrate thorium directly
with EDTA using Thorin did not provide sufficiently sharp
end-points. Titrations were made at pH 2.0 to 2.5 and pH 3
with just thorium originally present, and at pH 4.5 to 5-0
and pH 2.0 with 0.50 ml. lanthanum added for the end-point
reaction.
A second series of thorium titrations with more freshly
prepared EDTA and lanthanum solutions produced better re
sults. The initial slight pink color was present even when
Thorin was added to the solution of thorium and excess EDTA.
58
The end points were poor under all conditions tried (Table
l4). The last titration was of a larger excess of EDTA.
These results averaged 112.9 mg. thorium found, which
was 0.35% higher than calculated. The high experimental find
ings can be explained by the reaction
La+3
MnY"2 + LaY-1 + Ind™n > 2 LaY™1 + Mnlnd2~n
(3.3)
61
Determination of aluminum
Because of the scarcity of simple volumetric methods a
special effort was made to obtain a good volumetric determi
nation of aluminum by the lanthanum back titration of excess
EDTA. Some chemical similarities of aluminum and lanthanum
suggest that there may be advantages to such a method. The
tendency of aluminum to hydrolyse is probably a significant
cause of difficulty. The hydrolysis reaction would compete
with the chelating reaction of EDTA. The quantitative evalu
ation of this is subject to correct identification of the
chemical species and the availability of the pertinent data.
Latimer and Hildebrand (106) and Moelier (133) state that
aluminum probably precipitates as a gell forming Al^OyB^O,
or AIO(OH), and ages to Al^^B^O, or A1(0E)^. In 1955,
Szabo, Csanyi and Kavai (18^) noted the solubility product
constants for aluminum hydroxide given in the literature
ranged from 10 ^ to 10 . By using data from titrations
of aluminum solutions with sodium hydroxide, they determined
62
o _A_
Kh " (ÂlY~]
r.w-i [ÔH
r™-i3
-]3 ~ (3-^'
Kf-Ksp
Kfc = I • . « « - <3.6)
1 13.10 +1 .18
1 13.06 2 .14
2 13.04 +0.5 .12
1 13.02 to .11
1 13.03 9 .10
+1.0
5 12.99 .07
i 12.97 .05
4 12.93 .01
i 12.92 ±o.5 .00
2 12.91 15 .01
2 12.90 .02
5 12.87 .05
l 12.84 -0.5 .08
1 12.82 to 2 .10
—1.0
l 12.59 -1.0 2 .33
l 12.51 •41
Average 12.92 0.081
Procedure
The precipitation of the rare earth fluoride was pat
terned after the procedure described by Popov and Knudson
(li|3). These men determined fluoride indirectly by precipita
tion of lanthanum fluoride from an acetate buffered solution.
The precipitate was coagulated on heating in the presence of
acetate ion. After separation, they precipitated the excess
lanthanum with cupferron and weighed the oxide after ignition.
While the insolubility of rare earth fluorides is at
tributed to high lattice energies (133, p. Ij26), acetate ion
seems to be necessary to obtain a coagulated precipitate from
solution. Meyer and Schulz (127) in 1925 investigated lantha
num as a precipitant for fluoride. They found that lanthanum
68
Determination
According to concentrations of the solutions as stand
ardized, the method provided a straight line relation of
fluoride found to fluoride taken with a slope of 1*02$.
Samples taken from three sources of fluoride could not be
distinguished over this range. Results are given in Table
18. These three sources of fluoride were analytical grade
sodium fluoride used in the developmental work, a new bottle
of analytical grade sodium fluoride, and sodium fluoride
prepared by the reaction of hydrofluoric acid and sodium hy
droxide. This preparation was carried out by adding lj.8%
hydrofluoric acid slowly to a stirred solution of sodium
hydroxide in a polyethylene beaker in an ice bath. The prod
uct was filtered on a medium sintered glass filter, washed
with ethanol, and transferred into a watch glass to be dried
in an oven.
One to two percent high results were obtained in the
presence of silver, and up to 10% high with sulfate in fair
ly high proportions. It is suggested that these ions might
be used to precipitate other interfering ions. These effects
are shown in Table 19 and Table 20.
70
12 10.38
24 10.2-10.5 Poor end-point
48 10.1*1, 10.29
96 10.4-10.8 Turbid solution
71
0 10.35, 10.50
10 10.91, 10.94
lj.0 11.15, 11.15
80 11.28, ll.j+O
2-(l,8-DIHYDR0XY-3,6-DISIJIF0-2-NAPHTHrLAZ0)-
BENZENEARSOHIO ACID; ARSENAZO
Reagent
This compound, 2-(1,8-dihydroxy-3,6-disulfo-2-
naphthylazo)-benzenearsonic acid, was first prepared as one
of a series by Kuznetsov (91) in 19111. Its structural
formula is
73
,.rvH?
50.H
Purification
The indicator used in this investigation was purchased
from Eastman Kodak Company. It was a dark brown solid
claimed to be the dihydrate of the trisodium salt. On this
basis it reacted as 60% pure indicator. The material may
be used as received as a reagent for visual titrations and
colorimetric determinations. For characterization of the
reagent and its complexes, a purer product was desired.
A recrystallization procedure was devised from which a
product equivalent to nearly 100% tetraacid dihydrate was
obtained. This bright orange material precipitated when a
concentrated aqueous solution of the salt was added slowly
with stirring to concentrated hydrochloric acid. If too
much indicator solution was added so that the acid was di
luted a dark purple product was obtained instead. This has
not been characterized, but its equivalent weight corre
sponds to 97% pure trisodium salt dihydrate, or to lower
purity di- or monosodium salts. If obtained, this may be
redissolved in water, concentrated and reprecipitated.
The orange product was filtered, washed with acetoni
trile and dried at 110*. Excessive drying darkened it, but
apparently did not adversely affect it, since this material
75
Spectra
The absorption spectra of Arsenazo and its complexes
were taken to determine the optimum wave length and pH for
photometric titrations and spectrophotometrie determination.
The indicator spectra for several pH's are given in Figure
6. Within this range there was little pH effect. Other
spectra have shown that there was no change from pH Ij. to
pH 3, but that a twenty percent drop in absorbance occurred
between pH 8 and pH 9» The absorption peak remained at
500 iqi.
Spectra of the purple lanthanum and ytterbium complexes
are given in Figure 7 and Figure 8* They show that the com
plexes dissociated below pH 6. The lanthanum complex was
the only rare earth complex whose peak is slightly lower than
560 mp.. The uranyl complex (Figure 9) was blue between pH l\.
o>
Figure 6. Spectra of Arsenazo at pH 1}., pH 6 and pH 8, l.llj. x 10~^ M, 2.01 cm. cells
0.8
0.6
p H4
A 0.4 pH6
pH8
0.2
0.6
pHô
A 0.4 pH4
0.2
OJ
o
08
A 0.6
0.4
02
K. = = -W- (U.2)
c a ca
Photometric Titrations
at 570 mp, where the rare earth complexes were the absorbing
species. Other titrations did not produce as large absorb
ance changes measured at 560 and 550. iqi as at 570 mp..
Figures 11 and 12 depict titrations whose end-points
could have been detected visually. The curve of Figure 11
is for the titration of 35.97 rag. neodymiuia with 0.05193 M
88
o.s-
0.8
0.7
0.6
0.5
0.4
02
ml EDTA
0.9-
0.8
0.7
A
0.6
0.5
04
0.3
0.2
ml. EDTA
EDTA. and 35.97 mg» was found. The neodymium was 2.5 x
10"5 M, but the Arsenazo was only 10~^ M. The titrations
shown in Figure 12 were reduced in concentration one tenth
from the one shown in Figure 11, and they represent the
probable limit of visible detection. These were titrations
of 3.60 mg. of neodymium and 3.1(5 mg. of ytterbium with
4-.15 x 10"3 M EDTA. The amounts found were 3*57 and 3-60
mg. of neodymium and 3.38 and 3.lt5 mg. of ytterbium. Lit
tle difference between pH 6 and pH 7 was detected. Addi
tion of 0.1 M sodium nitrate in solutions 1 and I4. also made
little difference. The maximum in the curve for ytterbium
at pH 7 was observed a second time and was unexplained.
The shape of the curve illustrates the sharpness of the end-
point, which is clearly indicated as the complete disappear
ance of the complex color. The last six points of the
vertical portion were taken at 0.01 ml. increments from 1L.75
to I4..80 ml. titrant.
The effect of triethylenetetramine buffer was compared
with pyridine in the titrations of Figure 13. It is evident
that triethylenetetramine competes slightly with Arsenazo
for the rare earth. For both curves, 71.9 tig* neodymium
were titrated with 1.039 x 10"^ M EDTA at pH 6. Both titra
tions gave the same slightly high results of 71^.9 tig.
The regular and expanded instrument scale titration
curves are compared in Figures IJ4. and 15. The titrations
of Figure II4. were of ijj.l tig. of ytterbium and 36.0 p,g. of
91
0.8
0.7
0.6
0.5
0.4
0.3
02
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
1.00
.90
A'M
.70-
.60-
50
40
.30
.20
.10
.00
0 2 3 4 5 6 7 8 9
ml. EDTA
n
Figure If?. Photometric titrations of 100 ml» 7«5 x 10*" M
neodymium with 1.0 x 10"^ M EDTA: upper curve
using the expanded instrument absorbance scale,
lower curve using the regular instrument
absorbance scale
94
.80-
.75-
.70-
t .65 •
z
3 .60-
.55-
.50-
,3C-
.25- 4A
.20-
.10-
48
J05-
I ml
J30_
ml. EDTA
0.40
0.50
0.20-
0.10-
ml. EDTA
CONCLUSION
Summary
BIBLIOGRAPHY
137. Mailer, R. H. Ind. and Eng. Chem., Anal. Ed. 11: 1-17.
1939.
138. Nichols, M. L. and Condo, A. C., Jr. Anal. Chem. 26:
703-707. 1954-
139. Nielson, J. P. and Dangerfield, A. D. Arch. Ind.
Health. 11: 61-65= 1955-
140. Osborn, R. H., Elliot, J. H. and Martin, A. P. Ind.
and Eng. Chem., Anal. Ed. 15: 642-646. 1943•
141. Parrish, M. C., Widmyer, H. H., Brunner, A. J. and
Matson, F. R. Anal. Chem. 19: 156-157. 1947.
142. Paulson, R. V. and.Murphy, J. F. Anal. Chem. 28:
1182-1184. 1956.
143. Popov, A. I. and Knudson, G-. E. Anal. Chem. 26: 892-
894. 1954.
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